JPS60161731A - Dispersant and composition of antimony oxide - Google Patents

Abstract

PURPOSE:To provide a dispersant of antimonoy oxide capable of stably dispersing antimonoy oxide in a hydrophobic solvent at a high concn., constituted of an oil soluble noinoic surfactant and, if necessary, an oil soluble anionic surfactant. CONSTITUTION:A dispersant of antimony oxide consists of an oil soluble nonionic surfactant and, if necessary, an oil soluble anionic surfactant and disperses antimony oxide in a hydrophobic solvent to enable the formation of a stable antimony oxide dispersed liquid composition. As the above mentioned nonionic surfactant, higher fatty acid alkanolamide is pref. used and, as the anionic surfactant, phosphoric ester or phosphonate is used. The stable antimony oxide dispersed liquid composition prepared by containing 0.05-30wt% of the above mentioned dispersant, 10-50wt% of antimony oxide such as Sb2O4 or Sb2O5 and the hydrophobic solvent is further diluted by the hydrophobic solvent so as to adjust antimony oxide to 0.1-10wt% to be used in fire retardant treatment.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to antimony oxide dispersants and compositions. More specifically, < relates to a dispersant and a dispersion composition in which antimony oxide is stably dispersed in a hydrophobic solvent at a high concentration.

Antimony oxide is used as a strong combustion agent for plastics and fibers, as a sealant, as an additive in the production of glass and ceramics, and as a raw material for glassy enamel. In recent years, it has been discovered that deterioration of the catalytic action by metals such as nickel can be prevented by depositing antimony oxide on catalysts for fluidized catalytic cracking of heavy petroleum fractions.

The method for depositing antimony oxide on the catalyst for fluid catalytic cracking is to dissolve organic compounds containing antimony in heavy petroleum fractions, which are the raw materials for fluid catalytic cracking, and subject them to a catalytic cracking reaction at high temperatures to convert them into inorganic antimony. A method has been adopted in which it is deposited on a catalyst.

However, in the second method, it is necessary to produce an antimony compound.Also, in order to dissolve antimony in petroleum distillates, the antimony compound must have a bulky organic group. However, there is a problem that the organic group has no effect on catalyst activity 1 or prevention of deterioration.

There is also a method in which antimony oxide itself is added to the catalytic cracking reaction system and deposited on the catalyst.

However, antimony acid is completely soluble in petroleum fractions, etc., so even if it is added, it will precipitate in the high line of the catalytic cracker and will not be effectively sent into the reaction system. It is not possible.

In addition, in order to prevent deterioration of the activity of the cracking catalyst, it is most effective to continuously add 10 to 200 ppm of antimony oxide to the heavy petroleum fraction, which is the raw material, to the catalytic cracking reaction system. However, it is very difficult to continuously add a certain amount of solid antimony oxide and disperse it effectively in the raw material.

The inventors of the present invention have carried out extensive research in order to solve the problem described in item 1. JJ G has arrived.

That is, the present invention is a dispersant of antimony oxide in a hydrophobic solvent (first invention), characterized by comprising a nonionic interface of oil-soluble f1:, an active agent, and sb, o, and 5.
antimony oxide selected from Wl' consisting of b2o,
It is characterized by containing a hydrophobic solvent and a dispersant consisting of 0.05 to 30% of an oil-soluble nonionic surfactant and, if necessary, an anionic surfactant, as a dispersant based on the weight of the composition. This is a stable antimony oxide dispersion composition (second invention).

Regarding the oil-soluble nonionic surfactant used in the present invention and the oil-soluble anionic surfactant used as necessary, oil-soluble means that it can be used at room temperature (or in a heated state) Something that dissolves almost transparently in (・i,
Therefore, when mixed at a temperature lower than room temperature, the oil may not be transparent to the oil described above, but may become cloudy, with no precipitation, or even phase separation.

Examples of the oil-soluble F1 nonionic surfactants include those mentioned above. In this activator, the alkylene oxide (hereinafter abbreviated as AU) includes C2~, AO such as ethylene oxy 1ζ (hereinafter abbreviated as EO) and/or propylene oxide (hereinafter abbreviated as I0).

CI] Higher fatty acid alkanolamide A reaction product of a higher fatty acid and an alkanolamine and its AO compound Higher fatty acid has 10 to 20 carbon atoms.
Preferably, fatty acids having 12 to 18 linear or branched chains include saturated fatty acids (lauric acid, palmitic acid, stearic acid, etc.), unsaturated Jlf fatty acids (oleic acid, linoleic acid, etc.), mixed fatty acids (coconut oil, etc.). alkanolamines include mono- or jetanolamine, mono- or dibrobanolamine; the molar ratio of acid and amine is usually 1:1 to 1:3, preferably 1:1-1:2. Specific compounds include beef tallow fatty acid monoethanolamide (1:1 to 2 types), stearic acid jetanolamide (1:1 type), and AU additives thereof.

[■] Polyhydric alcohol fatty acid ester, polyhydric alcohol such as glycerin, pentaerythritol, sorbitan, sorbitol, or its intramolecular anhydride and carbon number 10-
Esters with 20 fatty acids such as oleic acid monoglyceride, sorbitan stearic acid (mono, senuki or tri)ester, pentaerythritol oleic acid triester, etc.

[1] Polyoxyalkylene nonionic surfactants Compounds with a structure in which AU is added to active hydrogen-containing compounds (alkylphenols, alkylnaphthols, higher alcohols, higher fatty acids, higher fatty acid amides, higher fatty acid amines, etc.) are listed. Examples of alkylphenols or alkylnaphthols include alkylphenols having 6 to 20 carbon atoms, preferably 8 to 18 carbon atoms, (
An alkylphenol or an alkylnaphthol containing at least one, preferably 1 to 2, such as nonylphenol, dinonylphenol, and nonylnaphthol is used.

Higher alcohols include linear or branched natural or synthetic alcohols having 8 to 20 carbon atoms, such as tZF or I2-18, such as cetyl alcohol, oleyl alcohol,
Examples include stearyl alcohol.

Examples of higher fatty acid amides include fatty acid amides having 1 to 24 carbon atoms, preferably 12 to 22 carbon atoms, such as stearic acid amide and oleic acid amide. Examples of higher aliphatic amines include aliphatic amines having 10 to 20 carbon atoms, preferably 12 to 18 carbon atoms, such as cetylamine and stearylamine. The number of moles of AO added is usually 1 to 10.
Preferably it is 1-6. Specifically, the following can be mentioned.

(a) AU of polyoxyalkylene alkylaryl ether alkylphenol or alkylnaphthol
Adducts such as nonylphenol EO (2) (indicates an adduct of 2 moles of EO to nonylphenol. The same description will be used hereinafter), dinonylphenol EO (4), etc.

(b) Polyoxyalkylene alkyl ether AO adducts of higher alcohols, such as coconut oil jM original alcohol EO (5) and cetyl alcohol EO (3).

(c) Polyoxyethylene polyhydric alcohol higher fatty acid ester polyalkylene glycol (polyethylene glycol,
esters of polypropylene glycol (such as polypropylene glycol) and higher fatty acids or A O adducts of higher fatty acids, such as mono- or diesters of polyethylene glycol (molecule fil 400 ) and oleic acid, stearic acid EO(4), etc.

(d) Polyoxyalkylene high fgl jH fatty acid amide AU additive of higher fatty acid amide An example is stearic acid amide IDO (5) Oleic acid amide 1i', 0 (:
3) etc.

(PO) Polyoxyalkylene alkylamine high grade, Pilgrimage 1
A o 4q adducts of amines such as stearylamine EO (3) oleyl raremine EO (5) etc. (TV'l) Phosphate triester Higher alcohol or AO adduct of higher alcohol Phosphate triester For example oleyl alcohol Phosphate triester, isostearylflucol Iyo (3)
IJ Triester Nato.

Among the oil-soluble nonionic 1n1 activators, the most desirable are higher fatty acid alkanolamides.

Oil soluble 1 used as necessary in the dispersant of the present invention
As the anionic surfactant for ``-1'', the following can be used.

The salts used in this activator include alkali metals (sodium, potassium, etc.), alkaline earth metals (calcium, magnesium, etc.), ammonium, and amines (alkanolamines such as mono-, di-, or triethanolamine, dimethylethanolamine, mono- or diisopropanolamine, lower alkyl amines (eg, methylamine, ethylamide, etc.), and salts of two or more thereof. Preferred are amine salts and alkaline earth metal salts. AO is the same as A and 0 in the oil-soluble nonionic surfactant.

[1] Phosphate ester salt or phosphonate long chain alkyl phosphate ester salt, [number of carbon atoms is 11 and 6 to 20,
Phosphoric acid mono- and/or diester salts of preferably 12 to 18 saturated or unsaturated higher alcohols (cetyl alcohol, stearyl alcohol, oleyl alcohol, etc.), such as oleyl alcohol phosphoric acid monoester diammonium salts] Sai polyoxyalkylene Alkyl ether or polyoxyalkylene alkylaryl ether phosphate ester salt, (i) AO compound of saturated or unsaturated alcohol (the number of moles of 7J11 is usually 1 to 8) or an alkyl group having 8 to 12 carbon atoms. A phosphoric acid mono- or diester salt of an AU adduct (the number of moles added is usually 1-8) of an alkylphenol or alkylnaphthol (nonylphenol, dotesylphenol, dinonylphenol, etc.) having at least one, preferably 1 to 2 alkylphenols, such as Stearyl alcohol EO (
5) Phosphoric acid diester monopotassium salt, nonylphenol EO (5) Phosphoric acid diester monoethanolamine salt] 'Long chain alkyl phosphonate [long chain alkyl group (usually 6 to 24 carbon atoms, preferably 12 to 20 carbon atoms)] Phosphonate salts having an alkyl group (including an alkenyl group) such as a cetyl group or an oleyl group, or a monoester salt such as oleylphosphonate diethylethanolamine salt.

[11] Sulfonic acid salt (a) Sulfosuccinate ester fiber dialkyl sulfosuccinate salt (alkyl group has 6 to 20 carbon atoms, preferably 8 to 18 carbon atoms)
For example, +1-octyl group, 2-ethylhexyl group, 1
1-tesyl group, +1-dodecyl group, etc.) For example, di-2
- Ethylhexyl sulfosuccinate sodium salt, di-n-octyl sulfosuccinate calcium salt, etc.

(b) Alkylbenzene sulfonate An alkylbenzene sulfonate having one and/or a plurality of branched or linear alkyl groups, usually having 8 to 20 carbon atoms and preferably 12 to 18 carbon atoms, such as dodecylbenzenesulfonic acid. Sodium, calcium dodecylbenzene sulfonate, etc.

(c) Alkanesulfonic acid salts having an alkyl group usually having 8 to 20 carbon atoms, such as calcium tetratetylsulfonate (d) α-olefin sulfonate salts having an alkyl group usually having 15 to 18 carbon atoms; sulfonic acid sodium salt etc.

(po)lignin sulfonates (storium salts, calcium salts, etc.) petroleum sulfonates (calcium salts, etc.), etc.

l] Sulfate ester salt (a) Alkyl sulfate ester salt Straight chain and/or branched sulfate ester of saturated and/or unsaturated alcohol with carbon number usually 6 to 2 o and preferably 12 to 18 'AX % Tatoe is cetyl Alcohol sulfur NI2: r-ster calcium salt, stearyl alcohol sulfate sodium salt, oxo alcohol (C1, to C1), sonic acid ester jetanolamine salt with a side chain ratio of 50% or more, etc.

(+:I) Polyoxyalkylene alkyl sulfate salt carbon number is 6-2oIJ, T- or 12-1
8 linear and/or branched saturated and/or unsaturated alcohol adducts (the number of moles added is usually 1 to 10
Preferably, sulfate ester salts of 1 to G), such as cetyl alcohol EO (4) sulfate ester triethanolamine salt, stearyl alcohol EO (3) sulfate M ester calcium salt.

(c) Polyoxyalkylene alkylaryl ether sulfate salt AU adduct of alkylphenol or alkylnaphthol having at least one alkyl group having 8 to 12 carbon atoms (number of moles added is usually 1 to 10, preferably 1 to 6) sulfate ester salts, such as dino-megaphenol], i'0
(4) Sulfate ester triethanolamine carbon number 10
-20 saturated and/-1' or unsaturated fatty acid monoglyceride sulfate salts such as coco/glyceride sulfate ester sodium salts.

(e) Sulfuric acid oil, highly sulfuric acid oil, sulfated fatty acid ester and sulfur, phosphoric acid 0-1-r'll+, sulfated sodium salt of oleic acid, etc.

(f) Sulfated olefins such as sulfuric acid f-hysodium salt of α-olenoin having 1z to 18 carbon atoms.

(g) Higher fatty acid alkylolamide sulfate salt Saturated and/or unsaturated fatty acid alkylolamide sulfate salt having 10 to 20 carbon atoms, such as beef tallow fatty acid monoethanolamide sulfate ester jetanolamine salt (IV) Carboxylic acid Salts of saturated and unsaturated fatty acids and hydroxyl group-containing fatty acids having a carbon number of usually from i to 20, preferably from 12 to 18, such as triethanolamine laurate, calcium oleate, and the like.

oil-soluble nonionic surfactant and l(m (on surfactant f
The ratio of 1:agent can vary within a wide range, for example from 100:0 to 1:99 in weight ratio, preferably l0
0:0 to 20:80.

Hydrophobic finite solvents used in the present invention include petroleum fractions (gasoline, kerosene, light oil, heavy oil, etc.), 11-paraffinic solvents (n-paraffins of Ca-C11l, such as rhohexane, +1-hebutane, and C8 ~C+y11-
Mixed n~paraffinic solvents consisting of paraffin), isoparaffinic solvents (propylene tetramer, etc.), aromatic hydrocarbon solvents (toluene, xylene, naphthalene,
methylnaphthalene and mixtures of two or more of these), ketone solvents (methyl isobutyl ketone, dibutyl ketone, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), ether solvents (dibutyl ether, methyl butyl ether, etc.) , an alcoholic solvent (2-ethylhexanol, nonyl alcohol, dodecyl alcohol, etc.), and a mixture of these two tools. Preferred among these are petroleum fractions, 11-paraffinic solvents, isoparaffinic solvents and aromatic hydrocarbon solvents.

In the present invention, J! consisting of S 13204 and sb, o:! Among antimony oxide O selected from 'l', the most preferred is 81)205.

The antimony oxide used in the present invention is usually in the form of a powder, and its particle size is, for example, 5 mm or more, preferably 1 mm or less.

Containment of antimony oxide in the composition of the present invention -IIi
is 4. 'J is not limited to J, but is usually 01% to 60%, preferably 102 to 60%, based on the weight of the composition.
It is 50%. If the content of antimony oxide is less than 0%, the viscosity of the composition increases and handling becomes difficult.
becomes.

The content of the dispersant is not particularly limited, and even if it exceeds 30%, the stability of the dispersion composition may be improved even if the content exceeds 30%, based on the weight of the composition. There is no improvement effect and it is economically disadvantageous.

The amount of dispersant is 1.6% of the amount of antimony oxide in the composition.
It is desirable to vary it depending on the For example, it is usually 5 to 1oO%, preferably 20 to 5%, based on antimony oxide.
It's 0.

The content of the hydrophobic solvent is also not particularly limited, and based on the weight of the composition, ifQ is usually 20 to 998%, preferably tL<
is 40-90%. If the content of the hydrophobic solvent is less than 20%, the viscosity will be high and handling will be difficult.

The dispersion composition may also contain a small amount (by weight of the composition) if necessary.
Preferable results may also be achieved by including 10% (preferably 0 to 6%) of water based on 14).

In order to stabilize the dispersion of the dispersion composition, hydrophilic solvents such as monohydric lower alcohols (methanol, ethanol, propatool, phthanol, etc.), polyhydric alcohols (ethylene glycol, diethylene glycol, furopanediol, glycerin, pentaerythritol) are used to stabilize the dispersion of the dispersion composition. For example, lower amines (methylamine, ethylamine, etc.), alkanolamines (monoethanolamine, jetanolamine, triethanolamine, isopropanolamine, etc.) are included in the composition. This may lead to better results. In that case, the amount of IJ is determined based on the weight of the composition.
+ Usually 0 to 10%, preferably 0 to 6%.

The method for preparing the composition of the present invention is not particularly limited. For example, antimony trioxide, which is a common oxide of antimony, is suspended in water, hydrogen peroxide solution, next-stretched chloric acid and its Sl]tCL and/or sb,o by adding an aqueous solution of an oxidizing agent such as a salt and heating to perform an oxidation reaction.

1:L of a dispersion containing . If an excess amount of acid is used to remove water from the dispersion thus prepared, it is desirable to decompose the oxidizing agent in an appropriate manner after the oxidation reaction is complete.) The solid obtained is dried and ground. The desired dispersion composition can be obtained by adding the above hydrophobic solvent and dispersant to the antimony oxide obtained in step 2 and stirring and mixing.

1. As the stirring and mixing method, it is preferable to use a special machine such as a speed mill or a roll mill that has a pulverizing function, or a homomixer that has a turbulent flow function due to high-speed rotation.

In some cases, a slurry product obtained by reacting a triacid (hyantimony) with an oxidizing agent using water as a solvent may be heated to a temperature higher than the boiling point of water, for example, by adding a solvent and dispersant with a boiling point higher than that of water. A stable dispersion composition can also be obtained by removing water from the system using an appropriate method.

The composition of the present invention contains antimony oxide (1[,
The color can be changed depending on the type of solvent, type of dispersant, and amount of dispersion, but it is usually white or white.

It is a yellow or light brown opaque liquid, and if the content of antimony oxide is low, it becomes a translucent liquid with a burl-like luster.

The composition of Kibatsu 1su1 has very fine antimony oxide particles. The analogy is + (
10 (a microscopic nail with a 11' f ratio of 1, in many cases it is not possible to confirm the size even when observed with a microscopic nail with a 11' f ratio of 1. It is assumed that the size has reached 1 μ or less. The stability of the liquid composition is also good, generally from 0°C to +1
(Even at high temperatures of +-C or higher, the dispersion state is not broken, and even when left standing for a long time in chamber 711.V, there is almost no sedimentation of the dispersed particles.Furthermore, Even when diluting by adding a hydrophobic solvent such as a petroleum fraction, the dispersion state will not be affected and the dilution should be done to an arbitrary ratio (for example, so that the content of antimony oxide is usually 01 to 10% by weight). I can do it.

10. Since the composition of the present invention exhibits the following effects, it is very useful as an additive for preventing the deterioration of the activity of catalysts for fluid catalytic cracking of petroleum fractions.

In other words, when used as an additive to prevent deterioration of catalyst activity, heavy metals, which are raw materials for fluidized extraction cracking, are used.

Antimony oxide is added to the heavy petroleum fraction and introduced into the cracking reactor, but if the dispersion state cannot be maintained when added to the heavy petroleum fraction, antimony oxide may settle in the piping of the reactor or the piping may be damaged. However, with the composition of the present invention, such problems do not occur with the composition of the present invention.

Attempts have already been made to disperse antimony antimony into water or hydrophilic organic solvents, and practical application has yet to be achieved.
There are very few attempts to disperse it in hydrophobic organic solvents.

In the present invention, antimony oxide is replaced with antimony trioxide, which is generally widely used. As a result of research, it became clear that antimony trioxide was more suitable for use as a dispersant. We have found that oil-soluble nonionic surfactants exhibit far superior dispersion stability.

The present invention will be further explained below with reference to examples, but the present invention is not limited to these 11 examples.

Example 1 q, 'J' Publication No. 2-212'1g° and Japanese Unexamined Patent Publication No. 52-2?4'? ? 8i! of antimony pentoxide mentioned in the publication No. Antimony pentoxide was produced by oxidizing antimony trioxide with arsenic peroxide in accordance with the method described above.

Antimony trioxide (Sb20.) 1800F and water 4
8007 was heated to reflux in a OE Kolben equipped with a cooling tube. Add to this 30% hydrogen peroxide solution 14 f) O! i' was added dropwise, and after it' and j' were finished, aging was carried out for 2 hours. Cool this and 1! The aqueous suspension of antimony oxide (referred to as antimony pentoxide) was a white to pale yellowish white colloidal liquid.

The antimony pentoxide powder obtained by drying and pulverizing this colloidal liquid at 120°C for 2 hours was a white to slightly yellowish white powder and contained 672% of antimony.

Antimony pentoxide (powder) obtained in this way 3
0 P, xylene 1552 and oleic acid jetanolamide (i: type) 15! i' was placed in a 500 ml beaker and forcefully stirred for 15 minutes using a homomixer 10,000 II) 11]. The antimony pentoxide dispersion obtained by removing a small amount of undispersed matter remaining by centrifugation was used as the dispersion composition of the present invention. The second composition was a pale yellow-white colloid and contained 10 oz of antimony. In addition, almost no sediment was observed even after being left at room temperature for one month, and xylene,
It could also be easily diluted into petroleum fractions such as eaves oil at any desired ratio.

Example 2 Antimony pentoxide (powder) 609 obtained in Example 1 and 120 g of kerosene were mixed in a hall mill 400Ip111 for 12 hours.
Knead for a long time, then add oleic acid jetanolamide 202 and further ball mill at 400 rpm.
The mixture was kneaded for 12 hours.

The antimony pentoxide slurry obtained in this way was centrifuged to remove undispersed matter to obtain the dispersion composition of the present invention.
)t. This composition is a slightly yellowish white colloid with a kinematic viscosity of 10.
C1)S (25□C) Contained 186% as antimony.

Example; 3 Antimony pentoxide water prepared in Example 1 1" cloudy matter 807, aromatic solvent (round neck petroleum SW'N10) 170
9. Sorbitan oleate monoester + +1! /
and sodium dioctyl sulfocono monophosphate: 17 to 5 (l me: full pen G at 98°C to l
Of the liquid distilled at 34+'C, only water is removed from the system.
(It is thickened by 1τ. This is cooled and the dispersion composition of the present invention is made 1:1.) This composition showed good dispersion stability.

Example 1 Antimony pentoxide (powder) 22 obtained by 1!1 in Example 1
7. Aromatic solvent (round neck oil 5WA-r mouth O) 62 Y
s 71 (3f/, 7g beef tallow fatty acid jetanolamide and 3g calcium dodecylbenzenesulfonate
Put it in a 200 ml beaker and mix it with a homomixer 10,000 pt.
After forcibly stirring for 10 minutes at n, diethylene glycol 3
2 was added and stirred for an additional 2 minutes. Patent applicant: Sanyo Kasei Koimo Co., Ltd.

Claims (1)

[Scope of Claims] I. A dispersant for antimony oxide in a hydrophobic solvent, comprising an oil-soluble nonionic surfactant and optionally an oil-soluble anionic surfactant. 2, Sl), 0. and 5b2o, antimony oxide selected from the group consisting of, a hydrophobic solvent, and 0.05 to 30% of an oil-soluble nonionic surfactant as a dispersant based on the weight of the composition, and optionally an oil-soluble anionic surfactant. A stable antimony oxide dispersion composition comprising a dispersant comprising an activator. 3. The composition according to claim 2, wherein the nonionic surfactant is a higher fatty acid alkanolamide. 4. The composition according to claim 2 or 3, wherein the content of antimony oxide is 10 to 50% based on the weight of the composition. 5. The composition according to any one of claims 2 to 4, wherein the composition is diluted with a hydrophobic solvent. 6. The composition according to claim 5, which is diluted so that the content of antimony oxide is 01 to 10% by weight.